Novel quaternary ammonium carbamate antistatic agents



United States Patent 3,454,625 NOVEL QUATERNARY AMMONIUM CARBAMATE ANTISTATIC AGENTS Fred S. Eiseman, Jr., Maplewood, and Leslie M. Schenck, Mountainside, N.J., assignors to GAF Corporation, New York, N.Y., a corporation of Delaware N0 Drawing. Filed Apr. 3, 1967, Ser. No. 627,859

Int. Cl. C07c 125/06, 87/30; D06m 13/46 U.S. Cl. 260-482 6 Claims ABSTRACT OF THE DISCLOSURE Antistatic agents of the formula:

wherein R is an alkyl or alkaryl radical containing at least 7 carbon atoms; X is hydrogen, methyl, or ethyl; n is an integer from 1 to 10; R and R are alkyl or hydroxy alkyl radicals of 1-3 carbon atoms; R is a hydroxyalkyl radical of from 1-4 carbon atoms; and Y is an anion.

These antistatic agents, particularly useful for synthetic fibers, are prepared by condensing an alkyl or aryl polyalkyleneoxy chlorocarbonate with a substituted alkyl diamine with subsequent acidification and alkoxylation to produce the quaternary compound, the chlorocarbonate being prepared by the reaction of the corresponding hydroxy compound with phosgene.

The present invention relates to new and useful compositions of matter which function as antistatic agents when coated on synthetic and natural fibers, e.g., polyester fibers, acetate rayons, wool, polyolefins and the like, and to the method for their preparation. More particularly, the present invention relates to substituted carbamates exhibiting antistatic properties which are prepared by the condensation of alkyl and aryl polyalkyleneoxy chlorocarbonates with a substituted alkyl diamine followed by acidification and alkoxylation.

The commercial importance of the synthetic fibers industry has greatly emphasized the importance of antistatic agents and finishes since synthetic fibers, e.g., polyester fibers, acrylics, vinyls, etc., are notorious static electricity generators. While other fibers, e.g., cotton or viscose, do not generate the static electricity to any great extent under normal humidity conditions, and fibers such as acetate, rayon, and wool are only moderate generators, necessitating only some precautionary measures in the processing mill, e.g., a controlled high humidity, synthetic fibers such as mentioned above are not easily treated to control static electricity buildup.

While several non-durable finishes have been proposed which are moderately effective in eliminating static buildup on these synthetic fibers, few have been proposed which are completely satisfactory durable antistats. Most finishes employed to eliminate static buildup on synthetic fibers fall into the category of true surfactants although there is no really distinct similarity or correlation between surface activity and antistatic action.

In general, antistatic agents function in two ways, both of which improve the electrical conductivity of the fiber surface. Such antistatic agents are either reasonably good conductors of electricity themselves, or they are hygroscopic and help concentrate atmospheric moisture on the fibers.

The majority of antistatic agents fall into one of the following three categories: 1) polyhydroxy and polyethyleneoxy non-ionic compounds; (2) cationic, or neutral nitrogenous compounds with a hydrophobic moiety in their structure; (3) long-chain phosphates, phosphonates, or other oxygenated phosphorus derivatives. Additional types include sulfonated oils and ester emulsions, and other fiber lubricant emulsions which depend on the particular emulsifying agent used for their antistatic effect.

Long chain quaternary ammonium salts have a marked antistatic action and are widely used in this capacity. These quaternaries, in common with numerous antistatic finishes, are frequently used in combination with auxiliary agents which may themselves be antistats, or serve the secondary purpose of binding the finish to the fiber, as disclosed in U.S. 2,463,282. The water-insoluble salts of higher amines, together with polystyrene sulfonates, are described in U.S. 2,700,001 as nylon antistats. The use of phos phorus compounds in antistatic capacities is given in U.S. 2,575,382, 2,575,399, and 2,676,122. Hygroscopic salts, such as cyclohexylamine lactate, are disclosed in German Patent 840,694, while the use of polyethoxylated fatty acids and alcohols as antistatic agents for polypropylenes as well as fibers, is reported in U.S. 2,525,691.

In accordance with the present invention, it has now been found that certain compounds which incorporate a carbamate structure within the molecule, and more specifically, those derived from the chlorocarbonate of an alkoxylated primary or secondary alcohol, or alkylphenol, and a dialkylaminopropylamine, show excellent antistatic properties when applied to synthetic fibers. These novel carbamates impart not only the antistatic activity associated with both an amide linkage and that imparted by a quaternary configuration, but also the desirable antistat characteristics of a polyalkoxylated hydrophobe. Unexpectedly the combination of these chemical functions within the carbamate molecular structure provides an enhancement lacking through the simple admixture of non-ionic and amide type antistatic agents.

It is, therefore, a principal object of the present invention to prepare new and useful substituted carbamate antistatic agents.

A further object of the present invention comprises antistatic agents of enhanced effectiveness, which antistatic agents contain an amide linkage and a polyalkoxylated hydrophobe.

Yet a further object of the present invention comprises new and useful substituted carbamate antistatic agents derived from the chlorocarbonate of an alkoxylated primary or secondary alcohol or alkylphenol and a substituted alkyl diamine.

Still a further object of the present invention comprises a process for preparing new and useful antistatic agents which process comprises condensing an alkyl or aryl polyalkylenoxy chlorocarbonate with an alkyl diamine followed by acidification and alkoxylation.

Still further objects of the present invention will become more apparent from the following more detailed description of the invention.

The new and useful antistatic agents of the present invention correspond to the general formula:

wherein R is an alkyl or alkaryl radical containing at least 7 carbon atoms,

X is hydrogen, methyl, or ethyl;

n is an integer from 1 to 10;

R and R are alkyl or hydroxyalkyl radicals of 1-3 carbon atoms;

R is a hydroxyalkyl radical of from 1-4 carbon atoms;

and

Y is an anion.

Exemplary alkyl or alkaryl radicals for R include: heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecly, nonadecyl, eicosyl, docosyl, pentacosyl, etc., methylphenyl, ethylphenyl, butylphenyl, hexylphenyl, octylphenyl, nonylphenyl, decylphenyl, dOdecylphenyl, petadecylphenyl, octadecylphenyl, nondecylphenyl, etc.

Exemplary alkyl and hydroxyalkyl radicals for R and R include: methyl, ethyl, propyl, isopropyl, hydroxymethyl, hydroxyethyl, hydroxypropyl dihydroxypropyl, etc.

Exemplary hydroxyalkyl radicals for R include; hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, dihydroxypropyl, dihydroxybutyl, etc.

Exemplary anions for Y include: halides, chloride, bromide, iodide, phosphates, nitrates, sulfates, and the like.

The new and useful antistatic agents of the present invention are prepared by condensing an alkyl or alkaryl polyalkylenoxy chlorocarbonate with a substituted alkyldiamine followed by acidification and alkoxylation.

The alkyl or alkaryl polyalkylenoxy chlorocarbonate is prepared by reacting phosgene with a polyalkyleneoxylated aliphatic alcohol or alkylphenol under ambient conditions, in accordance with the following reaction:

In general, a substantially equivalent amount of the reactants is employed and the reaction is carried out by bubbling phosgene under the surface of the polyalkyleneoxylated aliphatic alcohol or alkylphenol until substantially all of the hydroxyl content of the reactants is converted into the chlorocarbonate as determined by infrared analysis or other suitable means.

The polyalkyleneoxylated aliphatic alcohol or alkylphenol is prepared by any conventional procedure so as to incorporate 1 to moles of alkylene oxide, e.g., ethylene oxide, propylene oxide, or butylene oxide per mole of aliphatic alcohol or alkylphenol. The alkyl or alkaryl polyalkyleneoxy chlorocarbonate prepared in Reaction I is further reacted with a substantialy equivalent amount of gamma dialkyl or dialkanol aminopropylamine to produce a substituted amide in accordance with the following reaction:

The substituted amide produced in Reaction II is quaternized by reaction with an alkylene oxide or hydroxysubstituted alkylene oxide in the presence of an inorganic acid. Such a reaction is represented as follows:

III

HY RO(CH2(FEO)nCONHCHICHICH2N\ alkylene oxide Reaction III above can be more precisely broken down into two separate reactions as follows: IIIa l Ro(oH,oH0 CoN11C ;oH;0H2N HY In the Reactions I, II, III, 111a and IIIb above, R, R R R X, Y and n are as previously defined.

In the preferred synthesis, a commercial straight chain aliphatic alcohol admixture comprising approximately 5% C11, C12, C13, C14 and C15 is reacted with an alkylene oxide using an alkaline catalyst at C. and 13O p.s.i.g. until one to ten moles of the oxide is added. In place of the alkaline catalyst, acidic catalysts such as BF H PO and the like can be used. Secondary alcohols such as Z-decanol, 3-decanol, 4-decanol, 3-dodecanol, -4-tetradecanol, fi-hexadecanol, and the like, or their admixtures as well as alkylphenols such as octylphenol, linear decyl phenol, branched dodecylphenol, etc., can be substituted for the primary aliphatic alcohol. The resultant alkyl or alkylarylpolyalkyleneoxyalkanol is then reacted with phosgene to form the corresponding alkyl or alkylarylpolyalkyleneoxy chlorocarbonate, and the latter compound converted to its carbamate by reaction with gamma dialkylaminopropylamine. This latter derivative is acidified and reacted with an alkylene oxide to form its quaternary ammonium salt.

The new and useful antistatic agents of the present invention have been found to have unexpectedly advantageous antistatic properties, particularly when applied to synthetic fibers, such as polyesters, acrylics, polyolefins, polyamides, etc. Such antistatic agents have been found to reduce and maintain the electrostatic charges for extended periods of time below a potential of 3 kilovolts.

The following specific examples illustrate the new and useful product and process of the present invention. These examples are for purposes of illustration only, and the present invention is in no way to be deemed as limited thereto.

EXAMPLE I (a) To a round bottom flask was charged a total of 288 parts by weight of an ethoxylate (av. app. 2.0 moles E0) of a C -C straight chain primary alcohol admixture calculated as a 209 mw. average and having the composition 5% C11, C12, C13, C14 and C15. The ethoxylate was agitated at ambient temperature (2030 C.) while phosgene was bubbled in under the surface over about 1.5 to 2.0 hours. Addition of phosgene was continued until examination of sample on IR showed essentially all absorption due to the hydroxyl group was eliminated. A total of 109 gms. phosgene (1.1 mole) were required.

(b) To a beaker equipped With agitator, two dropping funnels, thermometer and a pH meter were charged 500 ml. water and 91 gms. dimethyl propylene diamine (0.9 mole). These materials were agitated at room temperature while 316 gms. of the chlorocarbonate (0.9 mole) prepared in (a) and 30% NaOH were dropped in simultaneously over about 1 to 1.5 hours at such at rate as to maintain the pH between 10.0 to 10.5. A total of 141 gms. 30% NaOH was required. After all reactants were added, the batch was agitated 15 minutes at room temperature and then brought to pH 9.0 with CF. HCl. A total of 2.0 gms. were required. The product was then stripped of water at 40 mm. pressure and the residue was filtered. The yield was 293 gms.

(c) To a 1 liter 4-necked flask with joints clamped for Percent nitrogen 4.9 Theory 5.6

The product, in general, corresponds to the formula:

(d) The quaternary formed above was applied from MeOH/CCL; (520 mls./1000 mls.) solvent mixture to polypropylene and Dacron swatches at 1.25% application rate according to AATCC Standard Test Method 76- 1959.

The swatches were conditioned at 72 F. and 50% relative humidity for at least 24 hours and the resistivity measured. Results were as follows:

Log ohms/square Polypropylene Dacron Control 14. 64 13. 26

Quaternary carbamate 7. 77 7. 65

EXAMPLE II Percent Nitrogen 7.2 Theory 8.0

The products correspond, in general, to the formula -(d) The quaternary formed above was applied from MeOH/CCI (520 mls./ 1000 mls.) solvent mixture to Dacron and to cotton swatches at 1.25% application rate according to AATCC Standard Test Method 76-1959.

The swatcthes were conditioned at 72 F. and 50% relative humidity for at least 24 hours and the resistivity measured. Results were as follows:

Log ohms/square Dacron Cotton Control 13. 26 14. 24 Quaternary carbamate 7. 59 7. 90

EXAMPLE III Parts (a) and (b) were the sams as in Example I. (c) To a 1 liter 4-necked flask with joints clamped for slight pressure were charged 250 gms. (0.6 mole) of the above carbamate, 250 ml. H and 47.5 gms. H PO to bring pH to 3.0 to 3.5. Materials were agitated at 5060 C. and purged with N Ethylene oxide (36.5 gms. from cylinder) were added. A total of 24 gms. were absorbed.

The product was stripped to C. pot temperature under line vacuum and then filtered.

The weight of the final product was 147 gms.

Percent nitrogen 4.8 Theory 5.0

The product corresponded, in general, to the formula:

(d) The quaternary formed above was applied from MeOH/CCL, (520 mls./ 1000 mls.) solvent mixture to Nylon Faile and polypropylene swatches at 1.25% application rate according to AATCC Standard Test Method 76-1959.

The swatches were conditioned at 72 F. and 50% relative humidity for at least 24 hours and the resistivity measured. Results were as follows:

CHrCHaOH Log ohms/square Nylon falle Polypropylene Control 13.91 14. 64

Quaternary carbamate 7. 85 7. 80

EXAMPLE IV (a) To a round bottom flask was charged a total of 174 parts by weight of an ethoxylate (1.0 mole E0.) of octyl alcohol. The ethoxylate was agitated at ambient temperature (2030 C.) while phosgene was bubbled in under the surface over about 1.5 to 2.0 hours. Addition of phosgene was continued until examination of sample on IR showed essentially all absorption due to the hydroxyl group was eliminated. A total of 107 gms. phosgene (1.08 mole) were required.

(b) To a beaker equipped with agitator, two dropping funnels, thermometer and a pH meter were charged 300 ml. water and 91 gms. dimethyl propylene diamine (0.9 mole). These materials were agitated at room temperature while 213 gms. of the chlorocarbonate (0.9 mole) prepared in (a) and 30% NaOH were dropped in simultaneously over about 1 to 1.5 hours .at such a rate as to maintain the pHbetween 10.0 to 10.5. A total of 38 gms. 30% NaOH was required. After all reactants were added, the batch was agitated 15 minutes at room temperature and then brought to pH 9.0 with CF. HCl. A total of 3.0 gms. were required. The product was then stripped of water at 40 mm. pressure and the residue was filtered. The yield was 218 gms. Theoretical yield was 0.9 X 303=272 gms.

so the percent yield was 80.2.

(c) To a. 1 liter 4-necked flask with joints clamped for a slight pressure were charged 182 gms. (0.6 mole) of the above carbamate, ml. H 0 and 45 gms. H PO to bring pH to 3.0 to 3.5. Materials were agitated at 50-60 C. and purged with N Ethylene oxide (33 gms.

from cylinder) were added. A total of 21 gms. were absorbed.

The product was stripped to 110 C. pot temperature under line vacuum and then filtered.

The weight of the final product was gms.

Percent nitrogen 5.9 Theory 6.3

The product conforms, in general, to the formula:

CH3 [CBHHO cniorrzo coNnonicmomN cna 111F04- CHzCHaOH (d) The quaternary formed above was applied from MeOH/CCL, (52.0 mls./1000 mls.) solvent mixture to Dacron and Nylon Faile swatches a 2.5% application rate according to AATCC Standard Test Method 76- 1959.

The product corresponded, in general, to the formula The swatches were conditioned at 72 F. and 50% relative humidity for at least 24 hours and the resistivity measured.

Results were as follows:

(d) The quaternary formed above was applied from MeOH/CCL; (520 mls./ 1000 mls.) solvent mixture to polypropylene and Orlon swatches at 1.25% application rate according to AATCC Standard Test Method 76-1959.

The swatches were conditioned at 72 F. and the 50% relative humidity for at least 24 hours and the resistivity L hm 0g 0 s/Square 25 measured. Results were as follows: Dacron Nylon ialle Control 13. 26 13. 91 Quaternary earbamate 8. 92 9. 14

30 Log ohms/square EXAMPLE V Polypropylene Orlon (a) To a round bottom flask was charged a total of 38% 3-52 660 parts by weight of an ethoxylate (10.0 moles E.O.) Qua emary car a of nonylphenol. The ethoxylate was agitated at ambient temperature (20-30 C.) while phosgene was bubbled in under the surface over about 1.5 to 2.0 hours. Addition EXAMPLE VI of phosgene was continued until examination of sample on IR showed essentially all absorption due to the B th d b W g 1 g 2 50 g of h drox l rou was eliminated.Atotal of 112 ms. hosa 5 We're Prepare Y 61% 1 y y g p g p 40 antistat into tared 4 oz. WMSC clear bottles. The solvent gene (1.15 mole) were required.

(b) To a beaker equipped with agitator, two dropping funnels, thermometer and a pH meter were charged 1100 ml. water and 91 gms. dimethyl propylene diamine. (0.9 mole). These materials were agitated at room temperature while 650 gms. of the chlorocarbonate (0.9 mole) prepared in (a) and 30% NaOH were dropped simultaneously over about 1 to 1.5 hours at such a rate as to maintain the pH between 10.0 to 10.5. A total of 150 gms. 30% NaOH was required. After all reactants were added the batch was agitated 15 minutes at room temperature and then brought to pH 9.0 with CF. HCl. A total of 5.0 gms. were required. The product was then stripped of water at 40 mm. pressure and the residue was filtered. The yield was 596 gms. Theoretical yield was mixture (520 mls. methanol/ 1000 mls. carbon tetrachloride) was then added by volume, i.e., 99 mls. and 97 mls., respectively, to produce soluble, fluid, clear solutions in each case.

Preweighed and conditioned swatches (11x12 cms.). were immersed in the appropriate baths for one hour with good agitation. This agitation consisted of light shaking and swirling by hand. The swatches all appeared to wet nicely and uniformly. Removed swatches and allowed to drain back into bottle for about ten seconds, then hung under balance on a hook and adjusted to 100% pickup by lightly blotting with paper towels. All swatches were relatively easy to adjust to 100% pickup.

The finished swatches were then placed in the steam heated cabinet overnight at 50 C. before conditioning. 0 9 739=71 After a minimum of 40 hours conditioning at 50% RH. and 73 F., the resistance of each swatch was measo the percent yield was 84.0. sured front and back across the warp. The average of (c) To a 1 liter 4-necked flask with joints clamped these two readings on each swatch was then calculated for slight pressure were charged 475 gms. (0.6 mole) of to obtain log ohms/square that is recorded in the followthe above carbamate, 450 ml. H 0 and 99 gms. C.P. HCl ing table:

LOG GEMS/SQUARE Percent application Nylon Polypropy- Dacron Orlon Composition applied bath Iai lens type 54 (T-42) Product Ex. 1 1. 25 8.18 7. 77 7. 8.10 2 50 7. 90 7. 43 7. 45 7. 73 Product Ex. II 1 25 s. 15 7. s4 7. 59 7. 90 2. 50 7. 69 7. 62 7. 41 7. 78 Product Ex. III 1. 25 7.85 7. so 7. 52 a. 05 2. 5o 7. 7. 49 7. 21 7. 62 Catanac l 1. 25 7. 49 8. 56 7. 16 8. 19 2. 50 8.33 8. 27 7. 99 s. 27 Control 13. 91 14. 64 3. 26 14. 24

1 Commercial antistatic agent of cationic type.

3,454,625 9 10 EXAMPLE VII R is a hydroxyalkyl radical having from 1 to 4 carbon Samples of the product of Example III were submitted Y riltoms; i for resistivity measurements. The first sample was ap- IS an q proximately 60% active in the mixture of isopropanol Anantlstatlc compound of the formula and water in which it was prepared while solvents had CH3 the SBCOI'ld sample, and ll. WaS essen- QIFISHHHO. (GHZCH2O)ZCNHCHQCHZOHQN CH3 01- 1a y 0 ac we.

The samples were applied at the 1.25% level from isopropanol solutions in 4 oz. WMSC bottles to Nylon An antistatic compound of the formula. Falle, polypropylene, Dacron (Type 54), and Orlon (T- 42) fabrics. These isopropanol solutions were slightly hazy, so repeat applications were made from solutions l2-15H25310(CH2 H207CNHCH2CH2 H2N H3 N 03" containing 70 g. isopropanol and 30 g. water. The prod- CHOHZOH ucts were completely soluble in this mixture, giving clear solutions. 4. An antistatic compound of the formula:

CH3 II C11-15H25-31O CH2CHzO/CNHCHzCHzCHzNCH HzPOr ornomorr 5. An antistatic compound of the formula:

in the steam cabinet overnight, and then conditioned at CHzCHZOLl',NHCHECHZCHWZCE HaPOr The samples were adjusted to 100% wet pick-up, dried I: 0 CH OBHI7O 73 F. and RH. for measurement of resistivity.

The absolute pickup was measured by weighing the con- CHCHZOH 6. An antistatic compound of the formula:

CHzOHaOI-I ditioned swatches before and after treatment. The data are recorded in the following table.

Nylon faile Polypropylene Dacron (type 54) Orlon (T-42) Percent by Percent by Percent by Percent by Concentration in application wt. on Log wt. on Log wt. on Log wt. on Log bath, percent fiber ohms/sq. fiber ohms/sqfiber ohms/sq. fiber ohms/sq.

Applied from isopropanol:

While certain preferred embodiments of the present References Cited invention have been shown by way of specific example, UNITED STATES PATENTS it is to be understood that the present invention is in no way to be deemed as limited thereto but should be 0011- 2,626,876 1/1953 Games 117-1383 strued as broadly as all or any equivalents thereof. 2,721,208 10/1955 Lossee et 260' 482 XR What is claimed 2,998,445 8/1961 Stewart et a1 260-482 1. An antistatic compound of the formula: 3,359,303 12/1967 Coker at 260-482 LORRAINE A. WEINBERGER, Primary Examiner. E Q Y- i A. P. HALLUIN, Assistant Examiner.

X Ra

wherein: US. Cl. X.R.

R is a radical selected from alkyl and alkyaryl radicals 117 138.8, 139.5; 260-75, 93.7, 94.9

having at least 7 carbon atoms;

X is selected from hydrogen, methyl or ethyl;

n is a number from 1 to 10;

R and R are selected from alkyl and hydroxyl alkyl radicals having from 1 to 3 carbon atoms; 

